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Microwave-assisted transformations of lignin for value-added material applications
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-6313-8539
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The chemical diversity and structural complexity of lignin, an abundant biopolymer found in vascular plants, present a multitude of opportunities for the modification and fine-tuning of its properties to suit downstream demands. In this thesis, microwave-assisted strategies were explored as efficient and environment-friendly pathways for lignin valorization towards value-added material applications. First, the mild microwave-assisted organosolv extraction of lignin from spruce wood was demonstrated. The effective deconstruction of lignocellulosic structures by microwave irradiation led to the rapid extraction of structurally intact lignin with preserved β-aryl ether linkages and minimal condensation. The high structural quality of the obtained lignin was visibly manifested in its significantly lighter color relative to most technical lignins, hence improving its suitability for material applications wherein the color of the end product is important. Next, a green approach to convert lignosulfonate to carbonaceous products was implemented via microwave-assisted hydrothermal carbonization. This resulted in the synthesis of carbon spheres that served as precursors for nanographene oxide (nGO)- type carbon dots, which were characterized as having abundant oxygen- containing functional groups. The nGO-type carbon dots were utilized as building blocks in the development of porous composites for the adsorption of metal ions and cationic dye pollutants. Lastly, microwave-assisted esterification was employed to both hydrophobize alkali lignin and to functionalize the microwave-extracted organosolv lignin with methacrylate units to facilitate their utilization for 3D printing applications. Through this microwave-assisted approach, high degrees of substitution were achieved after a short reaction duration without the need for additional solvents or catalysts. Effective hydrophobization was exemplified in the enhanced thermal stability and compatibility of the hydrophobized lignins in polylactide (PLA), thereby enabling the melt-processing of up to 50 wt% of lignin in PLA thermoplastic blends for fused filament fabrication. Also, successful functionalization of microwave-extracted organosolv lignin with reactive methacrylate moieties enabled it to partake in network formation within a photocurable resin for digital light processing. This ultimately resulted in 3D printed thermosets with improved tensile strength (by 15%) and elongation at break (by 79%) relative to unfilled resin, after the incorporation of just 1 wt% lignin.

Abstract [sv]

Lignins komplexa struktur med dess mångfald av kemiska bindningar möjliggör modifiering och finjustering av dess egenskaper. I denna avhandling presenteras strategier för miljövänliga och effektiva mikrovågsassisterade metoder som syftar till att öka lignins värde som material. Först utvecklades en mild mikrovågsassisterade organosolv-extraktion av lignin från gran. Mikrovågsbestrålning ledde till en effektiv sönderdelning av lignocellulosa och en snabb extraktion av lignin med en välbevarad struktur, med mycket liten kondensation. Den höga kvalitén syntes på dess betydligt ljusare färg jämfört med tekniska ligniner, därmed ökar användbarheten i applikationer där färgen på slutprodukten är viktig. Därefter utvecklades en metod för att omvandla lignosulfonat till kolprodukter genom mikrovågsassisterad hydrotermisk karbonisering. De syntetiserade kolsfärerna användes sedan för tillverkning av nanografenoxidkolprickar med många syreinnehållande funktionella grupper. Kolprickarna användes därefter som byggstenar i porösa kompositer för adsorption av tungmetalljoner och katjoniska färgämnesföroreningar. Slutligen användes mikrovågsassisterad esterifiering för att hydrofobisera alkali-lignin och för att funktionalisera mikrovågsextraherad organosolv-lignin för användning i 3D-printing. På kort tid uppnåddes höga substitutionsgrader med hjälp av den mikrovågsassisterade funktionaliseringen utan att ytterligare lösningsmedel eller katalysatorer användes. En effektiv hydrofobisering var tydlig genom en ökad termisk stabilitet och kompatibilitet med polylaktid, vilket möjliggjorde extrudering av filament och påföljande 3D-printing av blandningar med upp till 50 vikt% lignin. Genom funktionalisering av mikrovågsextraherad organosolv-lignin med reaktiva metakrylatgrupper kunde lignin inkorporeras som en egenskapshöjande del av 3D-printade och UV-härdade nätverk. Material med endast 1 vikt% lignin hade en högre draghållfasthet (15%) och förlängning vid brott (79%) jämfört med nätverk utan lignin.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2023. , p. 78
Series
TRITA-CBH-FOU ; 2023:24
Keywords [en]
lignin, microwave-assisted processes, organosolv fractionation, esterification, fused filament fabrication, digital light processing
Keywords [sv]
lignin, mikrovågsassisterade strategier, organosolv-fraktionering, förestring, additiv tillverkning
National Category
Natural Sciences
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-326519ISBN: 978-91-8040-595-9 (electronic)OAI: oai:DiVA.org:kth-326519DiVA, id: diva2:1754618
Public defence
2023-06-09, F3, Lindstedtsvägen 26, via Zoom: https://kth-se.zoom.us/j/65937305427, Stockholm, 09:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council, 2018-03451
Note

QC 2023-05-09

Embargo godkänt av tf skolchef Amelie Eriksson Karlström via e-post 2023-05-08

Available from: 2023-05-09 Created: 2023-05-04 Last updated: 2023-11-01Bibliographically approved
List of papers
1. Carbonized lignosulfonate-based porous nanocomposites for adsorption of environmental contaminants
Open this publication in new window or tab >>Carbonized lignosulfonate-based porous nanocomposites for adsorption of environmental contaminants
2020 (English)In: Functional Composite Materials, ISSN 2522-5774, Vol. 1, no 1Article in journal (Refereed) Published
Abstract [en]

Carbon-based adsorbents possess exceptional adsorption capability, making them an ideal platform for the remediation of environmental contaminants. Here, we demonstrate carbonized lignosulfonate (LS)-based porous nanocomposites with excellent adsorption performance towards heavy metal ions and cationic dye pollutants. Through microwave-assisted hydrothermal carbonization, a green approach was employed to carbonize lignosulfonate to carbon spheres. The LS-derived carbon spheres were then oxidized into nanographene oxide (nGO) carbon dots. A facile two-step procedure that involved the self-assembly of nGO and gelatin into a hydrogel precursor coupled with freeze-drying enabled the construction of three-dimensional (3D) free-standing porous composites without the use of organic solvents or chemical crosslinking agents. The favorable pore structure and abundance of surface functional groups on the nGO/gelatin porous composite proved to substantially facilitate the adsorption of Cu(II) in comparison to conventionally-used activated carbon. Further enhancement of adsorption performance was achieved by introducing additional surface functional groups through a non-covalent functionalization of the porous composite with lignosulfonate. The presence of negatively-charged sulfonate groups increased the Cu(II) equilibrium adsorption capacity (66 mg/g) by 24% in comparison to the non-functionalized nGO/gelatin counterpart. Both functionalized and non-functionalized composites exhibited significantly faster adsorption rates (40 min) compared to many graphene- or GO-based adsorbents reported in literature. In addition to the adsorption of heavy metal ions, the composites also demonstrated good adsorption capacity towards cationic dyes such as methylene blue. This paves the way for a high value-added application of lignin in environmental remediation and opens up new possibilities for the development of sustainable materials for adsorption and water purification.

Place, publisher, year, edition, pages
Springer Nature, 2020
National Category
Chemical Engineering Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-281241 (URN)10.1186/s42252-020-00008-8 (DOI)
Note

QC 20220426

Available from: 2020-09-16 Created: 2020-09-16 Last updated: 2025-02-18Bibliographically approved
2. Microwave Hydrophobized Lignin with Antioxidant Activity for Fused Filament Fabrication
Open this publication in new window or tab >>Microwave Hydrophobized Lignin with Antioxidant Activity for Fused Filament Fabrication
2021 (English)In: ACS Applied Polymer Materials, E-ISSN 2637-6105, Vol. 3, no 7, p. 3538-3548Article in journal (Refereed) Published
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-299858 (URN)10.1021/acsapm.1c00438 (DOI)000672740300027 ()2-s2.0-85111387997 (Scopus ID)
Note

QC 20210820

Available from: 2021-08-18 Created: 2021-08-18 Last updated: 2025-08-28Bibliographically approved
3. Lignin nanoparticle-enhanced biobased resins for digital light processing 3D printing: towards high resolution and tunable mechanical properties
Open this publication in new window or tab >>Lignin nanoparticle-enhanced biobased resins for digital light processing 3D printing: towards high resolution and tunable mechanical properties
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-326686 (URN)
Note

QC 20230509

Available from: 2023-05-08 Created: 2023-05-08 Last updated: 2023-05-09Bibliographically approved
4. Microwave-Assisted Organosolv Extraction for More Native-Like Lignin and Its Application as a Property Enhancing Filler in a Light Processable Biobased Resin
Open this publication in new window or tab >>Microwave-Assisted Organosolv Extraction for More Native-Like Lignin and Its Application as a Property Enhancing Filler in a Light Processable Biobased Resin
Show others...
2023 (English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-326688 (URN)
Note

QC 20230509

Available from: 2023-05-08 Created: 2023-05-08 Last updated: 2023-05-09Bibliographically approved

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Yao, Jenevieve G.

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